Lubricating composition



Patented Mar. 19,1946

UNITED STATES PATENT oFFic.

Luamcn'rmc comosmon 1.1mm Alfred Evansand John Sootchford Elliott, Beaconsfleld, England No Drawing. Application May 12, iota serial No. I

phosphite esters.

In this specification the expression "hydroxy-j substituted aromatic compound containing arc--- 442 ,71s. In Great mai rame 25, 1941 12 Claims.

This invention is for improvements in or relating to lubricating compositions, and is part cularly concerned with lubricating compositions t at are employed in internal combustion engines and that are subjected to high bearing loads and temalso increase its corrosive eiiect. On the other-,.

handmany additives which function as corrosion inhibitors have no value as extreme-pressure agents. The problem is of particular importance in the lubrication of modern internal-combustion engines employing bearings of the composite metal type such as are employed in aircraft. I

It is the object of the present invention to provide a new class of lubricatingv oil addition agents which are effective to reduce the corrosive action. of the oil upon such composite metal bearings and at the same time to increasejthe film-rupture strength.

According to the present invention, a lubricatiing composition comprises a lubricating oil base in which there is dispersed a small proportion of an organic compound consisting of an organic ester containing trivalent phosphorus derived from a hydroxy-substituted aromatic compound containing aromatic radicals coupled through sulphur.

In this specification and in the claims the expression organic ester containing trivalent phos-' phorus is restricted to phosphite esters and thiomatic radicals coupled through sulphur includes hydroxy-substituted aromatic thioethers; distill.- 'phides or polysulphides.

Thus according to the present invention, a lubricating composition comprises a lubricating oil base in which there is dispersed a small propor j tion of an organic compound consisting of a phosphite or thiophosphite ester derived from an arc-.1

(or tags) or polysulphide. Such compounds'may have one or more atoms of sulphinand one or more atoms (normally one or two) of phosphorus in the mole- ,cule and may be represented by the general iormula: v 5 X -O-R'(S)a-M wherein R a an aromatic radical, X is an organic radical containing trivalent phosphorus, M is an aromatic residue and n is a positive integer. More specifically such compounds may be represented by the general formulae:

wherein R and R are aromatic radicals, X and Y are organic radicals containing trivalent phosphorus, and n is a. positive integer, normally 1 to 4. Particularly useful are theadditives which contain in the molecule two atoms of trivalent phosphorus and which possess the general formula wherein R1, R2, R5 and Rs are the same or different and are aromatic, aliphatic or cycloaliphatic hydrocarbon radicals which maybe unsubstituted or or by halogen atoms, R3 and R4 are aromatic radlcalapreferably the same; which may also be substitut'edj e: "g. by alkyl; ester or hyd'roxyl groups or halogen atoms, and A may be oxygen or sulphur. If desired, R1 and R: may together form part of a I ringstructure; the radicals R5 and Rs may togetherior n part of a ring structure. such compounds may be obtained by reacting an aromatic v lfi mr substituted thioether disul hide or pol isulphid'e withphosphorus trichloride and a. phe- "jnolfalcohol, thiophenol thloalcohol or with a mix- ;ftureb! such compoundsin the requisite propor- I *tion's. Incertain cases suitable materials can be matic hydroxy-substituted thioether, disulphide cocbtained anaromatic -hydroxy-substituted substituted e. g. by alkyl or ester groups or com- 1 plex groups containing further atom or sulphur,

thioether and phosphorus trichloride only; such will have the general formula:

in which the radicals R consist of hydrocarbon CH; CH: CH: (1) l I on r01, o-r-o 21101 n 350 grams of"cresylic acid" (mixed o-mand p-cresols) were added. The mixture was refluxed gently in a large flask until no more hydrogen chloride was evolved (about 2 hours).

To the cooled mixture was then added a solution of 269 grams of di(3-carbomethoxy-4-hydroxyphenyl) thioether in 300 cc. of carbon tetrachloride, 190 grams (50% excess) of dry pyridine were then added, and the mixture refluxed for a further 15 minutes.

After standing overnight, the solution was decanted from the crystalline pyridine hydrochloride, filtered through muslin, and subjected to distillation in vacuo to remove carbon tetrachloride and excess pyridine. The residue was finally heated to 110 C. in vacuo. By this method 650 grams (9'7 per cent) of-a viscous red-yellow liquid were obtained.

The two reactions which take place may be represented as follows:

groups. The benzene nuclei may carry further 'substituents; a preferred substituent is the carbomethoxy group present in both nuclei and resulting from the employment of di-(3-carbomethoxy-4-hydroxyphenyl)-thdoether in the aforesaid reaction. For the radicals R it is at present preferred to employ the higher aliphatic (e. g. butyl and higher aliphatic groups) and aromatic groups. Specific examples of the radicals are n-butyl, amyl, Z-ethyl hexyl, oleyl, phenyl, o-mand p-cresyl, tertiary butyl cresyl and halogenated phenyl groups.

In place of di-3-carbomethoxy-4-hydroxyethers e. g. pp'-di-hydroxy-diphenyl thioether, di(2-methyl-4-hydroxyphenyl) thioether, di(2:4- dihydroxyphenyl) thioether and the thioethers derived from p-tertiary butyl phenol and p-tertiary amyl phenol.

Methods for the preparation of lubricating oil addition agents of the present invention will readily suggest themselves to one versed in the art. However, the following examples are given by way of illustration:

(A) COMPOUNDS OF GENERAL FORMULA (1) EXAMPLE I 221 grams of phosphorus trichloride were dissolved in 500 cc. of dry carbon tetrachloride, and

CHI 1 CEO 0 C phenyl thioether may be employed other thio- The second reaction only takes place on heating in the presence of pyridine or other acid binding agent. Certain other thioethers, however, can be induced to react in the absence of such a basic material. It will readily be seen that t such reactions may give rise to minor amounts of products other than those of the type specified in the foregoing formulae. Thus, in the first part of the reaction a small amount of tricresyl phosphite will invariably be formed and a corresponding quantity of monocresyl phosphorus dichloride, which in the second part of the reaction, will give rise to polymers of varying length by reaction with the thioether. Similar polymers are produced in bulk when 201' 3 mols. of the thioether are acted upon by 1 mol. of phosphorus trichloride, such a product having a very limited oil-solubility. When, however, they are found in minor-amounts mixed with the compounds of this invention, their presence is not objectionable.

Examine II 7.4 grams of butyl alcohol mixed with 8.5 cc. of pyridine were added gradually to a solution of 6.85 grams of phosphorus trichloride dissolved in 25 ,cc. benzene, and to this mixture was added a solution of 8.35 grams of di(3-carbomethoxy-4- hydroxyphenyl) thioether and 5 grams of pyridine in 30 cc. of benzene. After refluxing for 15 minutes the cooled solution was filtered from agaeasao 3 I pyridine hydrochloride and the distillation The equations areas follows:

efiected as in the previous example. I

-By this method were obtained 14.5 grams (841 (I) 01 C per cent) of a pale yellow liquid, less viscous than i 2 I +2110] the product of Example I. 5 H O P O The equations a e as follows: v

1 comm: PCi; c.mo-Poc.m 2H0] l ZHCl-i-ZCsHsN 2CaHaN-HC1 2Ho1+2c,m. N i zctmrmcl 9 (H) 01 G (0mm C(CIII): n cmooc coosm Q-ss-sQ- zc mo-dg-ocim noo-s-oonfi i, H g 0 Exmru: III v p p K x) J 6.2 grams of thio-p-cresol were added to a solution of 3.44 grams of phosphorustrichlori'de .The material was then worked up as in the two The structural formulae assigned to the com- EXAMPLE IV 7 Compound of general formula (4) To a solution of 3 grams of phosphorus trichloride in 30 cc. of benzene were added 5.6 grams Percentage 9 p Where phosphorus of o-chiorophenol and 5 grams of pyridine. The n diro Rl= R =iq-=Ri mixture was refluxed for 10 minutes to induce an 15 F d Cale. reaction. lated 4.64 grams of p-tertiary butyl phenol tetrasulphide were then added and 2.5 grams of pyflg g gg ggiggvy o yy 8 8-10 ridine, and the mixture refluxed fora futher 7 D o. o-Cresyl 7.89 7.54 10 utes DOHMHWIH. Tcrtiarlybutyl 5.88 5.93

cresy. The product was cooled, filtered and distilled- Blgyluitfi h .33 4 pp 1 y IOXY 1p cny 10k- Gl'. presy l0 7 as before By this method was Obtained hard Di(3-tcrtiary amyl-Ghydroxyphc- CyclohiaxyL 7. 17 19 soluble in mineral lubricating oil.

041190 0113000 000cm 0mm 15 in'80 cc. of benzene and the mixture refluxed 21101 +-2C5H5N ecnmurci until no more hydrogen chloride was evolved.

2.73 grams of pp-dihydroxydipheny1 {311 The foregoing are illustrative of the methods ether and 3 grams of pyridine were then added f Pr p available, b are n 0 Wise and the mixture refluxed a further 15 minutes. limitative.

previous examples. The product was an almost pounds claimed herein are conflrmedby analywhite solid of low melting point. sis, as the following examples show. (The The equations are as follows: method employed was Eschka'smethod):

(II) CH 3 110040011 CH: S OH:

yellow transparent resin which was, however, E p

r Y (B) COMPOUNDS OF GENERAL It will be observed that products prepared ac FORMULA (2) cording to the foregoing two examples will not These compounds are prepared similarly "but consist wholly of'the compounds of general forby employing; double the quantity of the thiomula (2) but will also contain a certain amount ether required for the corresponding compound of the corresponding compound of general .for-

of general formula '(1). mula (1) and an equivalent amount of unre- 'in 30 cc. of benzene and refluxed until no more v acted thioether. This last may be removed, at

. least in part, but it has not generally. been found 5.4 grams of fcresylic acid" were added to a necessary to do solution of 3.43 grams of phosphorus trichloride It should be noted that .althpugh thioethers hydrogen chloride was ev1ved such as di(3-carbomethoxy-4-hydroxyphenol) A solution f 335 grams f (u (3 carbomethoxy thloether will give satisfactory compounds of for- 4-hydroxyphenyl) thioether m 20 cc. benzene mule (5) the corresponding compounds of'eencontaining 3.5 grams of pyridine was then added em] type (1) containing two atoms of phosand the mixture refluxed for a further 15 minutes. phorus per molecule cannot be formed. Instead,

By this method there were obtained 12.8 grams long-chain polymers having a very low oil-solu- (88 per cent) of a yellow semi-solid mass. bmty are produced.

Percentage of phosphorus:

Per cent (C) COMPOUNDS OF GENERAL Found FORMULA (3) Calculated 5.36 r

The equations are as follows: These compounds can be obtained from uh- (I) TH: ilia OH 0P-0 e 11) CH: CH:

A cmooo 000.011;

o-r-o I cm -o crnooo 000.011; CHPOO 835 grams of m: j 4 am symmetrical thioethers such as phenyl p-llydroxphenyl thioether were dissolved in cc. hot car- YPhenYl thwether by reflctwns simllar to those bon tetrachloride containing 2.5 grams of pyalready n d. ridine, and a solution or 1.15 grams of phos- The addition agents of the present invention 3:22 gg ggg g ggg gg i gggfifig gg are particularly effective for improving the propproduct worked upmthe usual manner. 55 erties of a lubricating oil (for example, a par- There were bt 75 grams of hard Opaque afiinic mineral oil) These compounds, particuyellow solid. I larly those of general formula (6) in which the Percentage 0f phosphorus; Per cent radicals R. are aromatic radicals, are particu- Found 233 larly valuable in that they are readily oil soluble, Calculated e 3.01 so have a high decomposition point and possess the The equation is as follows: property of imparting a fairly high film-rupture 011,000 0000B; I strength to the oil in which they are dissolved. 3110 00K PCl Thus, 0.3 to 0.5% of many of these compounds will CHJOOO Coocm impart to a mineral oil a film-rupture strength 0 OH of 8,000 to 11,000 pounds per square inch or even higher when tested on the well-known Almen 011,000 000.011 type of testing machine. 0 0 311C! In other cases it may be desirable to employ.

I more than 0.5%. The following examples illus- Coo-cm trate the effectiveness of these compounds:

0 on In these tests the compounds were dissolved in mm H QCAHNHC, a paraffinic mineral oil of the distilled bright stock typenhaving itself a dim rupture strength or 4,000 pounds per square inch.

tioned. first, and the radical R1A (assuming R1=R1=R3=R4 following. Thus a compound oi f Where Fuu' Compound derived from- RI-Rv-RB-RI g? $833 I and is lbs/sq. in.

1. General formula (4): Percent Di(3-carbomethoxy-4-hydroxyphenyl) thioether Phenyl 3 s, 000 D0 1 Mixed cresols..- 0.3 10,000 Do 1 Butyl 0.3 9, 000 gp'Dihydroxydiphenyl thioether Phenyl 1. 0 115, 000 ii-tertiary amyl-B-hydroxy-phenyl) disulphide 2-eti1yl hexyl l 0 14, 000 2. General formula Di(3-ca1-bomethoxy-4-hydroxy-pheny1) thioether 0 5 16, 000

In addition, these compounds are inhibitors of corrosion and are therelore particularly suited for inhibiting the corrosion of composite metal bearings asis shown by the following tests.

type (4) in which R1A=phenyl and the thioether concerned is pp'dihydroxydiphenyl thioether, would be designated as p-p'dihydroxydiphenyl thioether phenyl phosphite.

011 under test Oi] uninhibited A+0.1% di(3-carbomethoxy-4-hydroxyphenyl) thioether butyl phosdi(3-carbomethoxy-4-hydroxyphenyl) thioether phenyl phosdi(3-carbomethoxy-4-hydroxyphenyl) thioether o-cresyl phost +81% di(3-carhomethoxy-d-hydroxyphenyl) thioether tertiary butyl oresyl phosp te dl(3carbomethoxy-4-hydroxyphenyl) thioether salicyl phose. +5.1? pp'dihydroxydiphenyi thioether phenyl phosphite ph phite phenyl hos hite.

+0.1% di 34:11: omethoxy-4-hydroxyphenyl) thioether cresyl (mixed) phosphite of general formula (2) +01% di(3-carbomethoxy-4-hydrdxyphenyl) thioether phosphite of general formula (5).

cm. internal diameter, each segment being equal in length to one quarter of the circumference of the bearing, were aflixed to the ends of vertical rods rotated at a speed of approximately 080 R. P. M. The rods were so adjusted that the segments were just immersed in the oil under test, 310 grams of which were contained in tall beakers of 1500 cc. capacity, heated to 160 C. ,in an oil bath. The surface of the oil made atangent to the arc of the circle of which the hearing was a segment. The oil bath was adapted to contain four such beakers so that four oils could be tested simultaneously. At the bottom of each beaker was placed a piece of sheet copper 3 X 11/41; x 31E- The hearings were detached and weighed an examined at intervals during the test, the loss in weight after certain specified time intervals being determined, graphically where necessary. The condition of the oils at the conclusion of the test was also noted visually.

In these tests a solvent refined mineral oil was employed (oil A) 0.1 per cent of the various phosphites being added in each case.

For simplicity in naming these phosphites they are assumed to be of general type (4) unless otherwise stated, the thioether or polysulphide from which they are derived being men- +0 pp'dlhydroxydiphenyl thioether oleyl phosphite +0.1 pi'dihydroxydiphenyl thioether p-cresyl thio phosphite +0 HEX-tertiary amyl-fi-hydroxyphenyl) disulphide cyclohexyl +0.11% diGti-tertiary amyl-B-hydroxyphenyl) disulphide Z-ethyl hexyl p 05 +0.1% di(3-tertiary butyl-G-hydroxyphenyl) tetrasulphide o-chloro- Welght loss of bearlng'iifter---- li ali l is Solid at 160 0.

Nil N11 Nil Nil 1 2 0111111111.

Nil Nil Nil N11 1 4 Do.

Nil Nil Nil Nil Do.

Nil 4 18 Solid at 160 C. Nil 1 2 s 011 fluid.

-- a: 1 2 Nil 1 e on solid at 0.

Nil 1 4 11 Solid (l30hours atl60 0. Nil N11 Nil Nil 1 0111mm.

Nil N11 Nil Nil 3 Do.

1 a 5 1s 25 011 501111 at 160 0.

It has also been found that the addition agents of the present invention do not increase the oxidation of a mineral oil under the conditions of the well-known oxidation test.

Furthermore the compounds of this invention 55 have a marked capacity for reducing oxidation under the conditions of the iron oxidation test.

In this test six gram samples of the oil under test are mixed with 0.1 gram of fine iron filings in petridishes and heated for a specified time in 60 an oven at C. After the oxidation the comparative viscosities are measured by mean of a standard microviscometer, the percentages of matter insoluble in petroleum ether (B. P. below 40 0.) determined on weighed quantities of the 5 oil (2-3 grams) in the normal way, and the acidities compared by adding neutral alcohol to the filtrates from the latter determination and titrating with standard alkali using phenolphthalein as indicator.

The following results clearly show the oxida,

tion inhibiting propertie of the'compounds of this invention.

rosion tests, already described. The oils were heated at 180 C. for 9 hours.

In this test oil B, a blend of a poor quality green cylinder oil with a naphthenic base oil of the 500 Red type, was employed. The test was of 6 hours duration.

Percentage ComparainsoLin gg Oil under test tivevlscospet.ether g m ity(70li.) a. P. P g

Percent Oil 13 uninhibited 13" 3. 20 143 +03% di(3-carbomethoxy-4- hydroxyphenyl) thioether o-cresyl phosphite 4' 28" 2. 22 120 +0.31% ppld hydroxydiv phenyl t ioether p-cresylthio phosphite 4 47" 2. 42 129 +03% di(3-tertiary am 1-6- I hydroxyphenyl)disulp ide cyclohexyl phosphite 4' 56" 2. 81 115 Tasr No. 3

In this test oil B, was again employed, the test 40 being or 6 hours duration,

oil-soluble phosphite ester effective to increase Advantage may accrue from the employment, in conjunction with the addition agents of the present invention, of substances, forexample certain esters, known to increase the oiliness of the composition.

In the formulae set out above, where the bond lin is shown extended into the benzene ring theindication is that the substituent in question may be attached atthat point or at any other available point in the ring.

We claim: I

1. The method of making a lubricating composition which comprises reacting an aromatic hydroxy-ester containing aromatic radicals cou pled through sulphur with an organic di-substituted phosphorus chloride compound to produce an oil-soluble phosphite ester effective to increase the film-rupture strength of a lubricating oil base in which it is dispersed.

2. The method of making a lubricating composition which comprises reacting an aromatic hydroxy-ester containing aromatic radicals coupled through sulphur with an organic di-substituteci phosphorus chloride compound in the presence of an acid-binding agent to produce an the film-rupture strength of a lubricating oil base in which it is dispersed.

3. The method of making a lubricating composition which comprises reacting an aromatic hydroxy-ester containing aromatic radicals coupled through sulphur with an organic di-substituted phosphorus chloride compound in the presence of pyridine to produce an oil-soluble phosphite ester effective to increase the filmrupture strength of a lubricating oil base in which it is dispersed.

' 4. The method of making a lubricating composition which comprises reacting an aromatic hydroxy-ester of the general formula HO (n) OH with a compound represented by the formula (R1A):PCl in which the radicals R are selected from the group consisting of alkyl, aryl, aralkyl and cycloalkyl groups, the radicals R1 consist of hydrocarbon groups, and A is selected from the group consisting of oxygen and sulphur,

. thereby forming an oil-soluble compound efiec- Percentage Comparainsol. in gg Oil under test tive viscospet.ether I ity 10 R. (up.

Per cm Oil B uninhibited 5 29" 3.62 165 +03% pp'dihydroxydi- .pheuy thioethcr oleyl phosphite 4'31" 2.73 145 +0.24% diSZ-methyl-ihydroxygheny) thioether amyl hydroxyphen l) thioether crcsyi (mixed phosphite of general formula (2) 4 27" 2.15 144 +0.53% di(3-carbomethoxy-4- I hydroxyphenyl) thioether plmsphite of general formule (5) 4 34" 2. 56 186 Again, the addition agents of this invention tend to reduce the carbon deposit in an internalcombustion engine as the following test results demonstrates. In this test, 0.5%" of the product of Example I was dissolved in a mineral oil and tested fo 12 hours in a motor cycle engine; a.

blank test was also performed; the results were as follows:

tive to increase the film-rupture strength of a lubricating oil base in which it is dispersed.

5. The method of making a lubricating composition which comprises reacting in the presence of an acid-binding agent an aromatic hydroxy-ester of the general formula 4 coon 11000 110 S9. OH

' lected from the group consisting of alkyl, aryl,

aralkyl and cycloalkyl groups, the radicals R1 consist of hydrocarbon groups, and A is selected from the group consisting of oxygen and sulphur, thereby forming an oil-soluble compound effec- 'tive to increase the film-rupture strength of a lubricating oil base in which it is dispersed.

6. The method ofmaking a lubricating composition which comprises reacting in the pres- 'with a compound represented byJthe formula position which comprises reacting an aromatic hydroXy-ester of the general formula (IZOOR ROOO with a compound represented by the formula (R1O) 2P--Cl in which the radicals Rare selected from the group consisting of alkyl, aryl, aralkyl and cycloalkyl groups, and the radicals R1 consist of hydrocarbon groups, thereby forming an oil-soluble compound efiective to increase the film-rupture strength of a lubricating oil base in which it is dispersed.

8. The method as claimed in claim 4 wherein the integer 2; equals 1.

9, The method of making a lubricating composition which comprises reacting di-(3-carbomethoxy-d-hydrcxyphenyl)-thioether with dicresyl phosphorus chloride to produce an oilsoluble phosphite ester effective to increase the film-rupture strength of a lubricating oil base in which it is dispersed.

10. The method of making a lubricating composition which comprises reacting equimolecular quantities of di-(3-carbomethoXy-4-hydroxyphenyl) thioether with dicresyl phosphorus chloride to produce an'oil-scluble phosphite ester effective to increase the film-rupture strength of a lubricating oil base in which it is dispersed.

11. The method as claimed in claim 10 wherein the reaction is conducted in the presence of an acid binding agent.

12. The method as claimed in claim 10 wherein the reaction is conducted in the presence of an acid binding agent.

ELLIOTT ALFRED EVANS. JOHN SCOTCHFORD ELLIOTT. 

